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New Technologies in Phenol Removal from Wastewater

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Wastewater containing phenol is generated in many of the steel industry’s coking facilities. Since destruction through burning is not only a bad alternative ecologically but also too costly due to the high water content, the preferred way is phenol recovery with simultaneous cleaning of the waste water until it can be discharged into the sewage treatment plant. A typical concentration for phenol in the effluent water is 6.8 wt%. Before this water can be released to the environment, the phenol concentration must be reduced to 39 ppb.

This section provides details on the latest developments and efforts in the removal of phenol from wastewater.

We have discussed the following:

  • Current Wastewater Treatment Process – Phenol Removal
  • New Technologies in the Removal of Phenol from Waste Water
    • Efficient Phenol Removal of Wastewater from Phenolic Resin Plants Using Cross Linked Cyclodextrin Particles
    • Using Adsorbent
    • Application of Pervaporation And Adsorption to the Phenol Removal from Wastewater
    • Membrane Techniques
    • Electrochemical Treatment of Wastewater Containing Polyaromatic Organic Pollutants
    • Continuous Electrochemical Treatment of Phenolic Wastewater in a Tubular Reactor
    • Solvent Extraction Process Development and On-Site Trial-Plant for Phenol Removal from Industrial Coal-Gasification Wastewater
    • Removal of Phenol From Aqueous Solution and Resin Manufacturing Industry Wastewater Using an Agricultural Waste: Rubber Seed Coat
    • Application of Pervaporation and Adsorption to the Phenol Removal from Wastewater
    • Removal of Phenol from Wastewater by Different Separation Techniques

Current Wastewater Treatment Process – Phenol Removal

Phenol proves to be a toxic chemical in the wastewater. Removal of phenol from wastewater is usually carried out by the extraction process. Phenol is stripped from the wastewater and the solvent is recycled for further use. The solvent is then treated biologically or by adsorption using carbon to eliminate phenol completely.

The process is shown below:

 

New Technologies in the Removal of Phenol from Waste Water

Efficient phenol removal of wastewater from phenolic resin plants using cross linked cyclodextrin particles

Removal of phenolic compounds from a raw industrial wastewater from phenolic resin processing, of which the components are phenol (8.9 wt%), m- and p-cresols (0.33 wt%), and xylenols (0.044 wt%), was carried out by using crosslinked cyclodextrin particles as a sorbent. A series of sorbents was prepared by varying the combination of cyclodextrin, the crosslinker, hexamethylene diisocyanate (HDI) or toluene-2,6-diisocyanate, and their molar ratio in the reaction batch. The removal of the phenolic compounds from raw industrial wastewater was an instantaneous process and was completed within about 5 min. The best removal efficiency was obtained by the crosslinked -CyD with HDI in a 1:8 molar ratio or the crosslinked Mix-CyD with HDI, also in a 1:8 molar ratio. The prepared sorbents were efficiently regenerated by elution of the adsorbed phenols from the crosslinked polymers with methanol.1

Adsorbent:

Amberlite™ XAD™4 polymeric adsorbent is used in several locations around the world to remove phenol from wastewater. Even high concentrations of phenol (20,000 ppm) in wastewater have been effectively treated. The resin's capacity for phenol increases with increasing phenol concentration. Regeneration of the resin is accomplished in several ways: 1% caustic or solvents such as acetone, methanol and formaldehyde. Acetone is frequently used since most phenol plants also have acetone production. Horseradish peroxidase was also found to be used for the removal of phenols and such toxic substances.2

Application of pervaporation and adsorption to the phenol removal from wastewater 
Application of pervaporation and adsorption to the removal of phenol from solutions modeling wastewater from phenol production with cumene oxidation process was investigated. The transport and separation properties of composite membranes PEBA, PERVAP 1060 and PERVAP 1070 in pervaporation of water–acetone, water–phenol and water–phenol–acetone mixtures were determined. It was found that all membranes were selective toward phenol. The PEBA membrane showed the best selectivity. However, this membrane is not actually available on the commercial scale. Thus, in the practical applications PERVAP-1060 and PERVAP-1070 could be used. Adsorption of phenol on the different Amberlite resins was also investigated. Among the Amberlite resins of various grades used, the Amberlite XAD-4 had the best properties in decontamination of aqueous phenol solutions. It was shown that regeneration of the adsorbent bed could be effectively performed with sodium hydroxide solution.3

Electrochemical treatment of wastewater containing polyaromatic organic pollutants

Disposal of industrial wastewater containing naphthalene- and anthraquinone-sulphonic acids by electrochemical methods has been studied in this paper. It was found that only a small fraction of the organics was oxidised by direct electrolyses, while complete mineralisation of the organics was obtained with the indirect process, electrogenerating hypochlorite from chloride oxidation. The effects of operating factors, such as anode materials and chloride concentration, were also investigated. The experimental data suggested that the Ti/Pt anodes had the highest electrocatalytic activity and increasing the chloride concentration in the electrolyte resulted in an increasing of COD and colour removal.4

Continuous electrochemical treatment of phenolic wastewater in a tubular reactor

The electrochemical treatment of phenolic wastewater in a continuous tubular reactor, constructed from a stainless steel tube with a cylindrical carbon anode at the centre, was investigated in this study, being first in literature. The effects of residence time on phenol removal was studied at 25°C, 120 g l−1electrolyte concentration for 450 and 3100 mg l−1 phenol feed concentrations with 61.4 and 54.7 mA cm−2 current densities, respectively. The change in phenol concentration and pH of the reaction medium was monitored in every run and GC/MS analyses were performed to determine the fate of intermediate products formed during the electrochemical reaction in a specified batch run. During the electrolysis mono, di- and tri-substituted chlorinated phenol products were initially formed and consumed along with phenol thereafter mainly by polymerization mechanism. For 10 and 20 min of residence time phenol removal was 56% and 78%, respectively, with 450 mg l−1 phenol feed concentration and above 40 min of residence time all phenol was consumed within the column. For 1, 1.5, 2 and 3 h of residence time, phenol removal achieved was 42%, 71%, 81% and 98%, respectively, at 3100 mg l−1phenol feed concentration. It is noteworthy that more than 95% of the initial phenol was converted into a non-passivating polymer without hazardous end products in a comparatively fast and energy-efficient process, being a safe treatment.5

Solvent extraction process development and on-site trial-plant for phenol removal from industrial coal-gasification wastewater

A phenol removal process was developed for the coal-gasification wastewater. Based on extraction principles and experimental results, an extracting solvent was selected in consideration of phenol removal, solvent recovery and COD removal for the coal-gasification wastewater. The extraction process conditions were studied, and a flowsheet for phenol removal was proposed. An on-site trial-plant of 2 t/h wastewater was set up for testing and industrial verification. The results of the on-site trials showed that more than 93% of the phenols and 80% of COD in the wastewater were removed. The operating cost of the proposed process was approximately balanced by the economic return of the recovered phenols.6

Removal of phenol from aqueous solution and resin manufacturing industry wastewater using an agricultural waste: rubber seed coat

Activated carbon prepared from rubber seed coat (RSCC), an agricultural waste by-product, has been used for the adsorption of phenol from aqueous solution. In this work, adsorption of phenol on rubber seed coat activated carbon has been studied by using batch and column studies. The equilibrium adsorption level was determined to be a function of the solution pH, adsorbent dosage and contact time. The equilibrium adsorption capacity of rubber seed coat activated carbon for phenol removal was obtained by using linear Freundlich isotherm. The adsorption of phenol on rubber seed coat activated carbon follows first order reversible kinetics. The suitability of RSCC for treating phenol based resin manufacturing industry wastewater was also tested. A comparative study with a commercial activated carbon (CAC) showed that RSCC is 2.25 times more efficient compared to CAC based on column adsorption study for phenolic wastewater treatment.7

Application of pervaporation and adsorption to the phenol removal from wastewater

Application of pervaporation and adsorption to the removal of phenol from solutions modeling wastewater from phenol production with cumene oxidation process was investigated. The transport and separation properties of composite membranes PEBA, PERVAP 1060 and PERVAP 1070 in pervaporation of water–acetone, water–phenol and water–phenol–acetone mixtures were determined. It was found that all membranes were selective toward phenol. The PEBA membrane showed the best selectivity. However, this membrane is not actually available on the commercial scale. Thus, in the practical applications PERVAP-1060 and PERVAP-1070 could be used. Adsorption of phenol on the different Amberlite resins was also investigated. Among the Amberlite resins of various grades used, the Amberlite XAD-4 had the best properties in decontamination of aqueous phenol solutions. It was shown that regeneration of the adsorbent bed could be effectively performed with sodium hydroxide solution.8

Removal of phenol from wastewater by different separation techniques

Application of membrane techniques (pervaporation and membrane-based solvent extraction) and adsorption tothe removal of phenol from solutions modelling wastewater from phenol production by cumene oxidation processwas investigated. The transport and separation properties of composite membranes PEBA, PERVAP 1060 and PERVAP 1070 in pervaporation of water-phenol mixtures were determined. It was found that the best removal efficiency ofphenol was obtained using the PEBA membrane. MTBE, cumene and the mixture of hydrocarbons were applied in the membrane-based phenol extraction. Extra-Flow contactor with Celgard X-30 polypropylene hollow-fiber porousmembranes was used in the experiments. MTBE was found the most efficient extractant. Adsorption of phenol on the different Amberlite resins was also investigated. Among the Amberlite resins of various grades used, the Amberlite XAD-4 had the best properties in the phenol removal from the aqueous solutions. It was shown that regeneration of the adsorbent bed could be effectively performed with sodium hydroxide solution.9

References

1Hirohito Yamasaki, Yousuke Makihata, Kimitoshi Fukunaga, 2006. Efficient phenol removal of wastewater from phenolic resin plants using cross linked cyclodextrin particles. Journal of Chemical Technology & Biotechnology81 (1271 – 1276).

2http://www.amberlyst.com/phenol_derivatives.htm

3Wojciech Kujawski, Andrzej Warszawski, W odzimierz Ratajczak, Tadeusz Por bski, Wies aw Capa a and Izabela Ostrowska2004. Application of pervaporation and adsorption to the phenol removal from wastewater. Separation and Purification Technology, 40 (123-132). 

4Marco Panizza, Cristina Bocca and Giacomo Cerisola, 2000. Electrochemical treatment of wastewater containing polyaromatic organic pollutants. Water Research, 34 (2601- 05).

5Bahadır K. Körbahti and Abdurrahman Tanyolaç, 2003. Continuous electrochemical treatment of phenolic wastewater in a tubular reactor . Water Research, 37 (1505- 1514).

6Chufen Yang, Yu Qian, Lijuan Zhang and Jianzhong Feng, 2006. Solvent extraction process development and on-site trial-plant for phenol removal from industrial coal-gasification wastewater. Chemical Engineering Journal, 117 (179- 185).

7Rengaraj S, Seung-Hyeon Moon, Sivabalan R, Banumathi Arabindoo and Murugesan V, 2002. Removal of phenol from aqueous solution and resin manufacturing industry wastewater using an agricultural waste: rubber seed coat. Journal of Hazardous Materials, 89 ( 185- 196).

8Wojciech Kujawski, Andrzej Warszawski, W odzimierz Ratajczak, Tadeusz Por bski, Wies aw Capa a and Izabela Ostrowska, 2004.  Application of pervaporation and adsorption to the phenol removal from wastewater. Separation and Purification Technology, 40 (123- 132).

9Wojciech Kujawski, Andrzej Warszawski, W odzimierz Ratajczak, Tadeusz Por bski, Wies aw Capa a and Izabela Ostrowska, 2004.  Removal of phenol from wastewater by different separation techniques. Desalination, 163 (287- 296). 



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